JPS59176295A - Manufacture of substituted trialkylsilyloxymalonic acid dinitrile - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing substituted trialkylsilyloxymalonic acid dinitrile. 1. Trimethylsilyloxymalonic acid dinitrile and its production method are already known. That is, dcyanotrifluoromethyl-(trimethyl7-lyloxy)-methane converts trifluoroacetyl chloride into trimethylsilyl cyanide 2
Other reactions of acid chlorides with trimethylsilyl cyanide described therein are for phoscene and oxalyl chloride. The reaction of acid halides with trimethylsilyl cyanide therefore appears to be limited to the highly reactive acid chlorides (Chem, IJe, r, 1
06 +587-593 (1973)).

However, it has also been disclosed that less reactive acid chlorides, such as acetyl chloride and benzoyl chloride, also react with trimethylsilyl cyanide to give the corresponding trimethylsilyloxymalonic dinitrile.

Nevertheless, the reaction proceeds only at elevated temperatures and when extra catalyst (Virison) is added. Yields of up to 85% are achieved (Ttttrah, edron Let
t,, 17 + 1449-1450 [1973
)).

It is also known that 2-(trimethylsilyloxy)-2-propenenitrile is obtained when carboxylic acid chloride is reacted with trimethylsilyl chloride. Furthermore β-
It is also known that when an acid chloride containing a hydrogen atom in position is reacted with trimethylsilyl cyanide in the presence of zinc iodide as a catalyst, the corresponding acyl cyanide is produced quantitatively. This acyl cyanide can be converted to sonitrile trimethylsilyloxymalonate by reaction with further trimethylsilyl cyanide in the presence of tetrabutylammonium iodite. Similar results are obtained when acid chloride is reacted with 2 mol of trimethylsilyl cyanide in the presence of tetrabutylammonium iodite. At this time, sonitrile trimethylsiloxymalonate can be separated with a yield of 78% (Ch, e
m, Ber.

115.263-87 (1982)).

The disadvantages of the known processes are that only very reactive carboxylic acid halides can be reacted with trimethylsilyl cyanide, or that the reaction has to be carried out in the presence of expensive catalysts or at elevated temperatures and in the presence of catalysts. This means that it will not happen.

This time, general formula I [wherein R1 represents optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl or optionally substituted heteroaryl, R2 represents C3-4 alkyl, and n represents an integer of 1 to 4] The substituted trialkylsilyloxymalonic acid sonitrile has the following formula: , and 11al represents fluorine, chlorine, bromine or iodine] with a trialkylsilyl/anido of the general formula ■ (R'')3SiCN N [wherein R2 has the abovementioned meaning] and -C ``reacting at least 2 moles per g mole of OHa, provided that the reaction is carried out, if appropriate, in the presence of an acid or base catalyst and the trialkylsilylnolide formed in the reaction is continuously removed from the reaction mixture, or b) In the first stage, the formula ■ 1 1i' (CHal) n
The acid halide of II in which R1, Rαl and n have the meanings given above is mixed with 2m trialkyl cyanide at a temperature of from 50 to 250°C in an amount of at least 1 molar equivalent per enemy ride group. reacting and removing the resulting trialkylsilyllide, and then reacting the reaction mixture with a further trialkylsilyl cyanide of formula (I) in the presence of a base at a temperature of -20 to 250°C, or C) An acyl cyanide of the formula ■ 1 RI (C-(:'A') rL■ [wherein R1 and n have the above-mentioned meanings] is reacted with a trialkylsilyl cyanide of 2m, provided that the reaction is or d) using a catalytic amount of base or acid, if appropriate, at a temperature of from -20 to +250 DEG C., or d) obtaining a substituted trialkylsilyloxymalonic acid sonitrile of the general formula I in which n is 1; O-COR' ■ 2i1tJ acyl cyanide of AI-C-CNv CN [wherein R1 has the abovementioned meaning], if appropriate, of the formula IV1 R1(C-CM) n■ where R1 has the abovementioned meaning and n represents 1], optionally in the presence of a catalytic amount of acid or base, with a triplekylsilyl cyanide of the formula m (R2), 5iCNI[l] Manufactured by a reaction process at +250°C.

The process according to the invention for the preparation of substituted trialkylsilyloxymalonic acid sonitrile of the general formula 1 differs from known processes in that it is universally applicable, ie limited only to reactive starting materials. ing. Furthermore, it can be carried out without expensive catalysts such as tetrabutylammonium iodite to give good yields. That is, the substituted trialkylsilyloxymalonic acid sonitrile of the general formula (1) can be obtained more easily and at a lower cost by using the method of the present invention than by known methods.

Process 1/i of the invention [Thus preferably prepared compounds of formula I are: R'C,~6 alkyl or 1d, Cs~1. Cycloargyl, particularly preferably C3_4 alkyl or C3_alkyl
cycloalkyl 1, with the proviso that these groups optionally include halogen, especially fluorine, chlorine or bromine, C5-4 alkoxy, especially methoxy or haethoxy, carboxyl, carbalkoxy, especially methoxycarbonyl or haethoxycargonyl, phenyl, phenoxy or thiophenyl. may be substituted with one or more identical or different groups from
In addition, the above phenyl ring is )-location or alkyl #
or R1 may further optionally be a halogen, especially chlorine, bromine or fluorine, nitro, CN, C, ~4 alkyl, especially methyl or ethyl,
C0-4-Lochenoalkyl, especially trifluoromethyl, trichloromethyl or pentafluoroethyl, 01-
4 alkoxy especially methoxy, ethoxy, C1-4 halogenoalkoxy especially trifluoromethoxy, fluorochloromethoxy or pentafluoroethoxy, methylenedioxy, ethylenedioxy, difluoromethylenedioxy, chlorofluoroethylenedioxy, fluoro Ethylenedioxy, C5-4 alkylthio, especially methylmercapto, C1-4 halo-alkylthio, especially trifluoromethylthio, 02-. Alkoxyalkyl, especially methoxymethyl, C29, halokenoalkyloxyalkyl, C7~, alkylmercaptoalkyl, especially methylmercaptomethyl, CI+v4alkylsulfonyl, especially dimethylsulfonyl, C1,4haloke9noalkylsulfonyl, carboxyl and carbalkoxy, especially methoxycarvinyl or represents phenyl or naphthyl, which may be substituted with one or more identical or different radicals from the group of ethoxycarponyl, or the radical C8-4-alkoxy-N=CB- especially CH,-0-A'=CH - or optionally halogen, C1~
4 represents alkyl or carboxyalkoxy having 2 to 4 carbon atoms, in particular phenyl, phenoxy or thiophenyl which may be substituted with carboxylmethoxy, or R1 is further heteroaryl such as bilisonyl, pyrimidinyl, trianonyl, inxazolyl, thiazolyl, oxadiazolyl, imidazolinope triazolyl , furanyl, and thiophenyl, provided that these may optionally contain halogen, especially one element, C1-4 alkyl%, methylethyl and C
8-4 alkoxy which may be mono- or polysubstituted with the same or different substituents from the group comprising in particular methoxy or ethoxy and may further be fused with one or more benzene rings; Chiru.

Compounds of formula I preferably prepared by the process of the invention include RI-1fic, ˜4 alkyl or halo (fluorine or chlorine in %), phenyl or phenoxy substituted C5_4 alkyl or C6˜, cyclo Alkyl or optionally halogen, especially fluorine or chlorine, C1-4 alkyl, especially methyl, C1,4 alkoxy, C1,4 halo-noalkoxy N
It represents phenyl which may be substituted with C1-4 halochenoalkyl, CB50-N=N- or nitro.

Compounds of the formula I which are very particularly preferably prepared are those in which R1 is identical or different substituents from the group comprising chlorine, fluorine, methyl, methoxy, trifluoromethyl, trifluoromethoxy and bromine. ' or phenyl optionally mono- or polysubstituted in the p-position.

The acid halide of formula (2) used as a starting compound in the process of the invention is known or can be prepared by known methods. The following acid chlorides are preferably used: niacetyl chloride, clopionyl chloride, pivaloyl chloride, cyclohexanecarboxylic acid chloride, benzoyl chloride, o+, m-1p-chlorobenzoyl chloride, 2.3-13 .4-13. ! 5-12
．． 6-12.4-dichlorobenzoyl chloride, 2,
3゜4-12.3.5-13,4,5-1-dichlorobenzoyl chloride, naphthalene-1-carboxylic acid chloride, o+, m-1p-nitropenzoyl chloride't o-1m-1p- ) trifluoromethylbenzoyl chloride, o +, m-1p-methoxybenzoyl chloride, 3,4-dimethoxybenzoyl chloride, 〇-, m-, p-trifluoromethoxybenzoyl chloride, 0-2m-, p-fluorobenzoyl Chloai)',' -+m-, p-bromobenzoyl bromide or baclorabachloride drol-4-bromobenzoyl chloride, 3-7" rom-4-chlorobenzoyl chloride, 3-chloro-4-methylbenzoyl chloride, 4 -chloro-3-methylbenzoyl chloride, terephthalic acid dichloride, phthalic acid dichloride, tetrahydrophthalic acid dichloride, 4-chlorophthalic acid dichloride, pyromellitic acid tetrachloride,
Pyridinecarboxylic acid chloride, thiophene-2-carboxylic acid chloride and 5-chlorothiophene-2-carboxylic acid chloride.

The trialkylsilylchlorides used as starting compounds in the reactions of the invention are known.

Preferably trimethylsilyl cyanide is used.

It can be obtained by reacting trimethylsilyl chloride with sodium cyanide (DE 3.018.821 and EP 40.356).

The silyl chloride or bromide produced in the process of the invention can be converted back to the trialkylsilyl cyanide of formula (2) by reaction with sodium cyanide.

Method α If benzoyl chloride and trimethylsilyl cyanide are used as starting materials, the course of the reaction of method α) can be represented by the following equation: 0- Si (CH
3) s N Process α) is carried out by mixing the two reaction components and heating the mixture to reflux temperature. The trialkylsilylnolide thus produced is traded.

However, the reaction begins by first introducing one of the two reactants (preferably the acid) into the reaction vessel and then warming the other reactant at a rate that allows the resulting trialkylsilyl halide to be removed by the fish box. Add while stirring. This reaction uses at least 2 equivalents of silyl cyanide equivalent to the equivalent of acid halide groups. A molar excess of 0.005 to 2 molar excess of silyl cyanide is preferred. The reaction rate is affected by this excess, especially if no further catalyst is used.

The reaction temperature can be varied within a substantial range. Generally it is between 0 and 250<0>C, preferably between 30 and 200<0>C, very particularly preferably between 60 and 150<0>C. The trimethylsilyl halide formed is preferably distilled off through a column during the reaction or at the end of the reaction.

The reaction is generally carried out under normal pressure. When using low-boiling aliphatic carboxylic acid chlorides, a slight increase in pressure may be advantageous. The reaction then takes place at a pressure of 1 to 10 bar, preferably 1 to 5 bar.
It is held in Pearl. It is also advantageous to carry out the reaction under reduced pressure so that the trialkylsilyl halide formed is completely removed.

Process a) is preferably carried out without addition of further catalyst.

However, acid catalysts may also be used. Acid catalysts that may be mentioned are Lewis acids such as aluminum chloride, iron chloride (■)
, antimony (V) chloride, boron trifluoride, titanium chloride (
■), zinc chloride, tin chloride (N), copper chloride (■), zinc iodide and mixtures of these compounds. Process a) may be carried out in the presence of a basic catalyst. Suitable basic catalysts which may be mentioned are tertiary amines, alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal cyanides and alkali metal or alkaline earth metal hydroxides. It is a salt of an organic acid of a metal. The following base catalysts may be mentioned as suitable: nitriethylamine, trimethylbenzylamine, viridun,
Tetramethylethylenesoamine, tributylamine, dimethylbutylamine, tetramethyl-1,3-butanesoamine, hexamethylenediethylenetriamine, tetramethyl-1,2-7'lohirenduamine, N-methylmorpholine, N,N'-nomethylpi veradun, N-methylhyherison, tetra, methylethylenesoamine, 1-
Tsumethylamino-3-formylaminopropane, quinoline, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, sodium carbonate, sodium acetate and mixtures of these compounds.

When using sparingly soluble catalysts, such as sodium cyanide, it is advantageous to add complexing agents or phase transfer catalysts, such as chlorinated steel or crown ethers.

The feature of process a) which is essential to the invention, namely the removal of the trialkylsilylnolide from the reaction mixture, can be carried out either continuously during the reaction or at the end of the reaction. The completion of the reaction can be detected by monitoring the reaction mixture in the IR spectrum (disappearance of absorption in the C-0 range in the IR spectrum). The reaction mixture is worked up in conventional manner, for example by distillation. Before carrying out this distillation, it is advantageous to neutralize any basic catalyst present, for example by adding benzoyl chloride to the reaction mixture. Further processing of the substituted trialkyl/lyloxomalonate dinitrile can be carried out by distilling off the trialkylsilyl halide formed during or after the reaction, followed by distilling off the excess trialkylsilyl cyanide, and discharging the reaction mixture as follows. It is often sufficient to use it in the reaction.

The acid or base catalyst used in the reaction is used in an amount of 01 to 5% by weight, preferably 0.5 to 3% by weight, based on the acid/hydrogen used. .

The reaction can be carried out in the presence of a diluent that is inert to the reactants and products. Such diluents that may be mentioned are hydrocarbons such as xylene and toluene, optionally substituted aromatics such as chlorobenzene or hanitrobenzene, tetramethylene sulfone and dinitrile methylglutarate.

However, the reaction is preferably carried out without diluent. Thus, for example, the starting materials may be heated together. When it reaches a relatively high temperature it melts 1-1, forming a homogeneous mixture.

Method b) Method f,, b) is characterized by the following equation: In method b), in a first step the acid no-ride is completely reacted with at least an equivalent amount of trialkylsilyl cyanide. The produced silylnolide is removed during or after the reaction, preferably by distillation. A substoichiometric amount of trialkylsilyl cyanide is then added to the reaction mixture in the presence of a catalytic amount of base.

The first stage of the reaction is 0-250°C, preferably 60-1
It is carried out at a temperature of 50°C. The second stage of the reaction is -20~
-1-250° (2, preferably [2 or -10~] -60°
The CX is particularly preferably carried out at a temperature of +10 to +40"C. In the second stage of process b), the base catalyst mentioned for process a) is used as base catalyst for that stage.

Process b) may be carried out in the presence of the solvents listed for process σ. Process b) is often carried out without a diluent; the second step of process b) comprises, in addition to the acyl cyanide, a small amount of unreacted trialkylsilyl cyanide or the resulting substituted trialkylsilylloquine of the general formula I. The reaction mixture obtained in the first stage, which may contain sonitrile malonate,
It may also be carried out by adding to a mixture of trialkylsilyl cyanide and a catalytic amount of base.

The process of method b) is surprising. That is, it is expected that the conversion of the intermediate acyl cyanide, which easily proceeds in the presence of a base, will give impurities (Angew et al.
, Chem, 68, 434 (1956)).

It is also surprising that the second stage of this reaction proceeds rapidly and quantitatively at low temperatures and without the addition of tributylammonium iodite.

The reaction mixture obtained after the second stage of process b3 can be used directly for further reactions, if necessary after removal of excess silyl cyanide. If one reaction mixture is worked up by distillation, it is also advantageous to neutralize the base, for example by adding benzoyl chloride for this operation.

Method C) When using terephthalic acid ducyanide and trimethylsilyl cyanide as starting materials for method C), the course of the reaction can be described by the following equation: 0S i (CM,
), the acyl cyanide of formula (2) which can be used as a starting material in method C) is known or can be produced by known methods. They can be obtained by reacting acid chlorides or acid anhydrides with alkali gold cyanides. Formula ■ derived from the acid halide listed in method a)
are preferably used in process C).

Method C) is generally carried out without diluent. However, the reaction may also be carried out using diluents that are inert to the products and reactants. One such diluent that may be mentioned is method α
These are listed in .

Process C) can be carried out in the presence of acid or base catalysts. Possible catalysts are the catalysts mentioned under process a). The catalyst is used in the same amounts as indicated for method σ).

The reaction time and reaction temperature can be significantly reduced by adding a catalyst.

The reaction is carried out between 0 and 250°C, preferably between 30 and 200°C, very preferably between 60 and iso°C.

If process C1 is carried out with base catalysis, the reaction conditions described under process b) are particularly suitable. The base-catalyzed reaction preferably proceeds at a temperature of 10-40°C.

Acyl cyanides and trialkylsilyl cyanides are used together in stoichiometric ratios in catalytic reactions. A slight excess of trialkylsilyl cyanide is advantageous. If no catalyst is used, it is advantageous to carry out the reaction at elevated temperatures and with an excess of 5 to 100 mol % trialkylsilyl cyanide.

In method C), the reactants are brought together in either order.

That is, the catalyst may be added to one of the two reactants together with the other. However, it can also be mixed with the two reaction components.

In the case of easily dimerized acyl cyanides, such as especially aliphatic acyl cyanides, the base medium M is preferably introduced first into the reaction vessel r together with the trialkylsilyl cyanide and then the acyl cyanide is added to this mixture.

Process C) is generally carried out under normal pressure. It is also advantageous for the reaction to proceed under slightly elevated or reduced pressure.

Method C) is preferably carried out at 10-40°C in the presence of a base catalyst.
carried out at a temperature of Particularly suitable basic catalysts in this case are the tertiary amines indicated for process α).

Method d) When using dimeric piparoyl cyanide and trimethylsilyl cyanide as starting materials for method d), the course of the reaction can be represented by the arrow equation: (C1i,) , C-C-0-C −C(CH,), +
2 (CM, , ), Sic'N-fN O5i (C1i, ).

2 (CH3), C-C-CMN Formula (V) gives a general definition of the 2i-acyl cyanide used in method d). These are known compounds and can be produced by known methods (Angew, Ch.
Em, 94, 13 (1982)).

The dimeric acyl cyanides of the formula V which form the carboxylic acid halides listed for process a) are preferably used in process d). Particularly preferred are compounds of formula V in which R1 is optionally substituted 90, ~, alkyl.

Dimeric acyl cyanide of formula (2) is often produced when producing monomeric acyl cyanide of formula (2). The latter are therefore often contaminated with dimeric acyl cyanides. It is believed that these dimeric acyl cyanides, which may be present as a mixture with monomeric acyl cyanides, can be converted to the desired substituted trialkylsilyloxymalonic acid dinitriles of formula -ff without expensive separations. This is a particular advantage of method d).

Process d) is preferably carried out in the presence of an acid or base catalyst. Possible catalysts are the base and acid catalysts mentioned for process α). However, this process can also be carried out without a catalyst.

When no catalyst or acid catalyst is used, the reaction ranges from -20 to +25
It is carried out at a temperature of 0°C, preferably 80-200'C.

If process d) is carried out in the presence of a basic catalyst, suitable temperatures are from 0 to 70°C, preferably at room temperature.

The dimeric acyl 7anide of formula (1) and the trialkylsilyl cyanide of formula (2) are used in stoichiometric amounts in process d). A 10 to 200 molar, % excess of trialkylsilyl cyanide is advantageous.

Process d) can be carried out in the presence of a diluent that is inert to the reactants and products. Diluents that may be mentioned are those listed for process α). However, the process in the absence of diluents is particularly preferred. If the reactants are solids at the beginning of the reaction, a homogeneous solution can be achieved by mixing the reactants without a diluent and, if appropriate, warming the mixture slightly. Process ct is preferably carried out under normal pressure. 7 However, it may also be carried out under an increased pressure of 1 to 10 par.

After carrying out the reaction, any excess amount of silyl cyanide is removed by distillation; the reaction mixture can then be used for the secondary reaction without further treatment.

As already mentioned, process d) is particularly preferably carried out under base catalysis. This allows the reaction to proceed substantially quantitatively.

The substituted trialkylsilyloxymalonate sonitrile of formula 1 prepared by processes α) to d) is an important starting material for the preparation of compounds with insecticidal and acaricidal activity 3, i.e.
They can be used for the preparation of the compounds known from DE 3,140,275.

The following examples illustrate the invention but are not limiting as to its practice.

Example 1 (Method a) O5i(CB,)3 L 2-chlorobenzoyl 5932 and zinc chloride 2f in 12
It was heated to 0-140°C and 693 v of trimethylsilyl cyanide was added dropwise, while the resulting trimethylsilyl cyanide was distilled off from a short column. Towards the end of the distillation, the bottom temperature was increased to 180-190°C and kept at this temperature for 1 hour.

The crude product was distilled, resulting in a boiling point of 1. , 3106-1
09°C pure O-chlorophenyltrimethylsilyloxymalonic acid sonitrile 4259f was obtained.

In addition to the desired product, the first distillate also contained O-chlorobenzoyl cyanide.

The following compound was also prepared analogously to Example 1: Example 2 0Si(CH,)3 Shizuku Na point: 155-60℃ 10.5 days Bg Example 3 0S i (CM, ), Crude product, broken down by distillation Example 4 0Si (CIi3)3 136-138℃/12 punishment Hg Example 5 (method α) O8i (CE,).

Cno1-O-CB-(?-CM CM 1052 g of methoxyacetyl chloride and 192 g of trimethylsilyl cyanide were stirred at 80-90°C for 30 minutes, then the temperature was slowly raised to 130°C, and the trimethylsilyl chloride was poured into a short column. The crude product was then distilled.

Methoxymethyltrimethylsilyloxymaronated dinitrile 125? I got it. Boiling point, 6:98-100+1c0 Example 6 (Method a) O5i (CM3).

Benzoyl chloride 2817 and trimethylsilyl cyanide 2187 were heated, and the generated trimethylsilyl chloride was distilled out from a 40 cWL Pigraw column.

Around the end of the A trade, trimethylsilyl cyanide was introduced into history.
The mixture was heated to reflux at about 150° C. for 3 hours. This was then subjected to an initial distillation. Dinitolyl phenyltrimethylsilyloxymalonate 47sr (gas chromatography = 96%) remained as bottom product.

Example 7 (Method b) Trimethylsilyl cyanide 4167 was converted to 3,4-sochlorobenzoyl chloride 852? was added to the solution at 8o-90'C, and upon further heating, the trimethylsilyl chloride produced and distilled off from the 20o Pigrau column. Lower the bottom temperature to 12
After raising the temperature to 0°C, an additional 100P of trimethylsilyl cyanide was added. When no more acid chloride remained in the bottom product (monitored by JR spectroscopy), the mixture was cooled, 2 ml of triethylamine was added at 20'C, and a further 3202 mL of trimethylsilyl cyanide was added dropwise without cooling. added to. This mixture was then heated at room temperature for 1
After stirring for several hours, it was confirmed by JR spectrum that the carbonyl absorption band no longer appeared.

After stabilization with 3 ml of benzoyl chloride, the product was subjected to an initial distillation.

1190 y of residue remained. It consisted of 98% sonitrile 3,4-dichlorophenyltrimethylsilyloxymalonate according to gas and chromatography. Distillation gave pure material 1130f'. Boiling point: 114-b Example 8 (Method C) 1 O5i (CD3)s 40 parts of 2,5-dichloropenzoyl cyanide and 201 parts of trimethylsilyl cyanide were heated to 195°C over 2 hours and stirred for 2 hours. .

Boiling point by distillation. , 2113~116°C and melting point 62~
Sonitrile 2,5-dichlorophenyltrimethylsilyloxymalonate at 64°C 39.5! tIl! Ta.

The following compound was prepared analogously to Example 8: Example 9 Example 10 CH30S i (CD3).

1 CH, C'N Terephthalic acid no cyanide 73.6 f and trimethylsilyl cyanide 190v to zinc chloride 1? At the same time, the temperature was slowly warmed to 160°C. After 1 hour, the reaction was completed and excess trimethylsilyl cyanide was distilled off using a vacuum knife. The spectral data indicated the presence of the desired substance. This could not be distilled without decomposition.

Example 12 According to Example 11 O5i (CD3)3 ■ was synthesized; this material could not be distilled.

Example 13 (Method C) 1 <ctt, n, , C-C-CN + (C1l,
), 5iCN ------111------;)
10Si (CB,,).

(CN3), C-C-CN CN trimethylsilyl cyanide 149 and triethylamine 1 mrp' were first introduced into the reaction vessel, then pivaloyl cyanide 190 ni was heated up to 40 °C with ice cooling.
was added dropwise. The mixture was then distilled under water pump vacuum. As a result, t-butyltrimethylsilyloxymalonic acid nonitrile 2932 was obtained. Boiling point, 4: 77
℃.

Example 14 (Method C) O5i (C'1i3).

Trimethylsilyl cyanide 200f, 3,4-dichlorobenzoyl cyanide 400v and triethylamine 1
．． 5- at a maximum of 30°C. Then add 1 of this mixture
The mixture was stirred for an hour; the carbonyl absorption band disappeared from the IR spectrum. According to the spectral examination, the residue is 3.4
- dichlorophenyltrimethylsilyloxymalonic acid dinitrile.

Hydrolysis of this product in concentrated sulfuric acid yielded 3°4-dichlorophenylhydroxymalonic acid diamide.

Example 15 (Method C) O5i(CM, )3 Sodium cyanide 0.31 and copper cyanide (1) 0.
14 was added to penzoyl cyanide 1312.

105 ml of trimethylsilyl cyanide were added dropwise at a maximum of 40°C. This mixture was then stirred at 40°C for 4 hours. In the JR spectrum, the C=0 absorption band was no longer visible. After distilling off the slight excess of trimethylsilyl cyanide, phenyltrimethylsilyloxymalonate sonitrile 2151 remained as a residue.

Example 16 (Method d) CM 0 11 (CB, l 3C-C-0-C-C (CD3) 8+
2 (CD, )s S iCN→■ CN O5i (C1l,).

2 (CH3)8-C-CN CM 0.4 ml of triethylamine was added to 314 ml of dimeric hivaloyl cyanide and 30 ml of trimethylsilyl cyanide at room temperature and the solution was stirred for 4 hours. In the IR spectrum,
The carbunyl absorption band was no longer visible.

Gas chromatography analysis of the control material showed that tert-butyltrimethylsilyloxymalonic acid dinitrile was produced.

Example 17 (Method d) Dimeric pivaloyl cyanide 1112 and trinotylsilyl cyanide 552 were heated to 190°C and then an additional 551 portion of trimethylsilyl cyanide was slowly added dropwise. As a result, the bottom temperature decreased to 153°C. The mixture was then distilled.

Besides a small amount of starting product, tert-butyl) IJ
150f of methylsilyloxymalonic acid dinitrile was obtained.

Boiling point, 4: 77-78°C.

Example 18 (Method α) O5i (CH3)5 Cinnamic acid chloride 33.3 f (0.2 mol) and trimethylsilyl cyanide 99p (t mol) WODABC
O (2,2,2-diazabicyclooctane) and mixed at room temperature. An exothermic reaction began after about 2 minutes, during which time the temperature rose to 48°C. The mixture was then stirred at 50°C for 30 minutes.

The trimethylsilyl chloride and excess trimethylsilyl cyanide formed were distilled at 50'C under water pump vacuum. Styryltrimethylsilyloxymalonic acid sonitrile 42f remained.

The use of DABCO was particularly advantageous when carrying out processes a) to d) of the invention. This allowed the reaction to be carried out at low temperatures. In this way, even sensitive starting compounds could be reacted.

Claims (1)

[Claims] 1. General formula I [wherein R1 represents optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aryl or optionally substituted heteroaryl, and R2 represents C1-4 alkyl, and n represents an integer of 1 to 4. α) In the production of substituted trialkylsilyloxymalonic acid sonitrile having the general formula n has the abovementioned meaning and Mal represents fluorine, chlorine, bromine or iodine].
has the abovementioned meaning] in at least 2 moles per mole of --COHal groups, provided that the reaction is carried out, if appropriate, in the presence of an acid or base catalyst and the reaction produced the trialkylsilyl halide is continuously removed from the reaction mixture, or b) in the first stage, a compound of the formula ■ R' (-C-Jlal) fLIf [wherein R',
Hal and n have the abovementioned meanings] is reacted with a trialkylsilyl cyanide of formula (I) at a temperature of 50 to 250°C in at least 1 molar equivalent per acid halide group, resulting in the formation of The trialkylsilyl halide is removed and the reaction mixture is then diluted with further trialkylsilylcyanil in the presence of a base.
or C) Formula ■ 1 R1(C-CN)n ■ [In the formula, R1
and n have the meanings given above].
of a trialkylsilyl cyanide, provided that the reaction is carried out, if appropriate with a catalytic amount of base or acid, from -20 to +
or d) if a substituted trialkylsilyloxymalonic acid sonitrile of the general formula I in which n represents 1 is obtained, the general formula ■ 0-COR' ■ R'-C-CNv ■ CN where R1 has the abovementioned meaning, if appropriate 21 R' (C-CN)ny, where R' has the abovementioned meaning and n is 1 ] as a mixture with the trialgylsilyl cyanide of SiCN lit, optionally in the presence of a catalytic amount of acid or base, at a temperature of -20 to +250°C. A method for producing substituted trialkylsilyloxymalonic acid sonitrile of general formula 1, which is characterized by the steps of: